Adhesive comprising post-chlorinated polyethylene and polyvinyl chloride

ABSTRACT

An adhesive composition particularly suitable for adhering polyvinyl chloride and an olefinic polymer comprising 1 to 99% by weight of post-chlorinated polyethylene having a mean molecular weight of about 20,000 to 200,000, a specific gravity of 1.00 to 1.35 and a chlorine content of 5 to 50% by weight and 99 to 1% by weight of polyvinyl chloride having a mean degree of polymerization of about 300 to 2,500.

This is a division of application Ser. No. 428,997 filed Dec. 27, 1973,now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a thermoplastic resin type adhesivecomposition and a method of using the adhesive composition. Moreparticularly, the invention relates to an adhesive compositioncomprising post-chlorinated polyethylene and polyvinyl chloride and alsoto a heat sealing method for polyvinyl chloride and olefinic polymerusing the adhesive composition.

2. Description of the Prior Art

Conventional adhesive compositions are generally classified into athermoplastic resin-type adhesive, a thermosetting resin-type adhesive,a rubber-type adhesive, and a natural adhesive. Strictly speaking, thenatural adhesive can be included in the above three-kinds of adhesivesfrom the viewpoint of the chemical structure but for the sake ofconvenience, the natural adhesive is classified as above. Theabove-described three kinds of adhesives other than the natural adhesiveare prepared synthetically and hence there are many types of adhesiveswithin each class of these adhesives.

Furthermore, in practically using such adhesives, they are usedindividually or as a mixture of two or three kinds of adhesives.Moreover, they are frequently used as a mixture thereof with suchadditives as solvents, fillers, extenders, etc.

Accordingly, the kinds of adhesives are almost innumerable with eachhaving different properties and they are used for their own individualpurposes. In other words, no such single universal type adhesive isknown which can be used for all purposes. In fact the most suitableadhesive for the specific purpose is used from a practical standpoint.

SUMMARY OF THE INVENTION

The inventors have, therefore, investigated various kinds ofthermoplastic resin-type adhesives and as the results thereof it hasbeen discovered that an excellent adhesive having a wide range of usescan be obtained by blending post-chlorinated polyethylene and polyvinylchloride.

An object of this invention is to provide a novel and inexpensiveadhesive mainly comprising polyvinyl chloride.

Another object of this invention is to provide a heat sealing methodusing this adhesive.

Still another object of this invention is to provide a compositematerial prepared using the adhesive.

That is, the present invention provides a solid-type adhesive comprising1 to 99% by weight of post-chlorinated polyethylene which has a meanmolecular weight of about 20,000 to 200,000, a specific gravity of 1.00to 1.35 and a chlorine content of 5 to 50% by weight, preferably whichhas a mean molecular weight of about 20,000 to 100,000, a specificgravity of 1.10 to 1.30 and a chlorine content of 25 to 40% by weight,and 99 to 1% by weight of polyvinyl chloride having a mean degree ofpolymerization of about 300 to 2,500, preferably 400 to 2,000, andfurther, the invention provides a liquid adhesive prepared by dissolvingthe above described solid adhesive of this invention in a solvent.

The term "mean molecular weight" used throughout the specification andclaims refers to a number mean molecular weight.

According to a further embodiment of this invention, there is provided amethod of adhering polymers using the above described adhesivecomposition. Still further, the invention provides a heat sealing methodof adhering an olefinic polymer and polyvinyl chloride without using anadhesive.

It is effective to select the blend ratio of post-chlorinatedpolyethylene and polyvinyl chloride in the adhesive of this inventiondepending on the materials to be adhered to each other. Further, theadhesive of this invention can adhere polyvinyl chloride and an olefinicpolymer by heat sealing without the necessity of any specific surfacepre-treatment, which has hitherto been considered to be difficult.

DETAILED DESCRIPTION OF THE INVENTION

Polyvinyl chloride and an olefinic polymer such as polyethylene,polypropylene, etc., have now been used in large quantities due to theirexcellent properties and their low cost.

The total amount of both polymers is far larger than the half of thetotal amounts of all plastics or polymers used practically at present.However, although it is possible to adhere an olefinic polymer andpolyvinyl chloride using an adhesive or adhesives, it is almostimpossible to heat seal the polymers since olefinic polymers aregenerally poor in polarity and are crystalline while polyvinyl chlorideis a polar material and is poor in crystallinity.

As methods of adhering an olefinic polymer and polyvinyl chloride,adhering the polymers with an adhesive or adhesives after activating thesurface of the olefinic polymer by the action of an organic peroxide,the irradiation with ionizing radiation, the action of an oxidizing gas,etc., are known. However, it has been impossible to heat seal olefinicpolymers and polyvinyl chloride without using some type of treatment asstated above and a third material.

Thus, the present invention also provides a method of heat sealing anolefinic polymer and polyvinyl chloride capable of adhering bothpolymers by only contacting and pressing them together under heatingwithout using any adhesive and without applying any surface activationtreatment to the olefinic polymer.

That is, in the heat sealing method for polyvinyl chloride and anolefinic polymer according to the present invention, the adhesion of thepolymers is conducted by bringing a polyvinyl chloride article intocontact with the olefinic polymer and pressing them together underheating, the polyvinyl chloride comprising a blend of from 2 to 50 partsby weight of post-chlorinated polyethylene having a mean molecularweight of about 20,000 to 200,000, preferably 20,000 to 100,000, aspecific gravity of 1.00 to 1.35, preferably 1.10 to 1.30, and achlorine content of 5 to 50%, preferably 25 to 40%, and 100 parts byweight of polyvinyl chloride having a mean degree of polymerization ofabout 300 to 2,500, preferably 400 to 2,000.

In the present invention, a co-extrusion method to form a co-extrudedcomposite material of polyvinyl chloride and an olefinic polymer in onestep using at least two extruders, an extrusion-lamination method toseal onto polyvinyl chloride an olefinic polymer extruded through anextruder, a press method in which adhesion of two components isconducted using a pressing machine, and the like can be employed.

It is well known that polyvinyl chloride can be blended withpost-chlorinated polyethylene to improve the impact resistance and theweatherability of the polyvinyl chloride but it is not known that anarticle comprising a blend of polyvinyl chloride and post-chlorinatedpolyethylene can be easily heat-sealed to an olefinic polymer.

The olefinic polymers which can be used in this invention include ahomopolymer of an olefin having less than 14 carbon atoms, such aspolyethylene, polypropylene, polybutene-1, polybutene-2,polyisobutylene, polypentene-1, polypentene-2, poly-2-methylbutene-1,poly-2-methylbutene-2, poly-3-methylbutene-1, etc.; a copolymer of theabove described olefins, such as an ethylene/propylene copolymer, anethylene/1-butene copolymer, an ethylene/1-hexene copolymer, anethylene/4-methyl-1-pentene copolymer, a propylene/1-butene copolymer, apropylene/1-hexene copolymer a propylene/4-methyl-1-pentene copolymer,etc.; a copolymer of more than 30% by weight of one or more of the abovedescribed olefins and one or more of other monomers capable ofcopolymerizing with the olefins, such as an ethylene/vinyl acetatecopolymer, an ethylene/acrylic acid copolymer, an ethylene/methacrylicacid copolymer, an ethylene/itaconic acid copolymer, an ethylene/maleicacid copolymer, an ethylene/acrylic acid/methyl methacrylate copolymer,an ethylene/itaconic acid/methyl methacrylic acid copolymer, anethylene/methacrylic acid/vinyl acetate copolymer, an ethylene/acrylicacid/vinyl alcohol copolymer, an ethylene/vinyl chloride copolymer, anethylene/styrene copolymer, an ethylene/vinylidene chloride copolymer,an ethylene/styrene/acrylic acid copolymer, an ethylene/methacrylicacid/acrylonitrile copolymer, an ethylene/vinyl chloride/acrylic acidcopolymer, an ethylene/vinylidene chloride/acrylic acid copolymer, anethylene/vinyl fluoride/methacrylic acid copolymer, anethylene/chlorotrifluoroethylene/methacrylic acid copolymer, etc.; agraft copolymer prepared by grafting to a polyolefin or anolefin-containing copolymer of an ethylenically unsaturated compoundcapable of being graft-polymerized thereto and containing the olefiniccomponent at more than 30% by weight, such as a polyethylene/acrylicacid graft copolymer, a polyethylene/methacrylic acid graft copolymer, apolyethylene/ethyl acrylate graft copolymer, a polypropylene/acrylicacid graft copolymer, a polypropylene/methacrylic acid graft copolymer,a poly-1-butene/acrylic acid graft copolymer, apoly-3-methylbutene/acrylic acid graft copolymer, anethylene/butene-1/acrylic acid graft copolymer, an ethylene/vinylacetate/vinyl chloride graft copolymer, etc.; an ionic copolymer, viz.,an ionomer resin prepared by the reaction of an ionic metal compoundwhich can be dissolved in water and a compound prepared from an α-olefinand an α ,β-ethylenically unsaturated carboxylic acid as anethylene/acrylic acid copolymer, an ethylene/methacrylic acid copolymer,an ethylene/itaconic acid copolymer, an ethylene/maleic acid copolymer,an ethylene/acrylic acid/methyl methacrylate copolymer, anethylene/methacrylic acid/ethyl methacrylate copolymer, anethylene/methacrylic acid/vinyl acetate copolymer, an ethylene/acrylicacid/vinyl alcohol copolymer, an ethylene/styrene/acrylic acidcopolymer, an ethylene/propylene/acrylic acid copolymer, anethylene/vinyl chloride/acrylic acid copolymer, a polyethylene/acrylicacid graft copolymer, a polyethylene/methacrylic acid graft copolymer, apolypropylene/acrylic acid graft copolymer, a polypropylene/methacrylicacid graft copolymer, a poly-3-methylbutene/acrylic acid graftcopolymer, etc.; and blends of two or more of the above describedhomopolymers of the olefins, copolymers of the olefins, copolymers ofthe olefins and monomers copolymerizable with the olefins, olefinicgraft copolymers, and ionomer resins.

The polyvinyl chlorides which can be used in this invention includevinyl chloride homopolymer; a copolymer of vinyl chloride and one ormore other monomers copolymerizable with vinyl chloride and containingmore than 30% by weight of vinyl chloride, such as a vinylchloride/ethylene copolymer, a vinyl chloride/propylene copolymer, avinyl chloride/vinyl acetate copolymer, a vinyl chloride/acrylic acidcopolymer, a vinyl chloride/vinylidene chloride copolymer, a vinylchloride/vinylidene chloride/acrylic acid copolymer, a vinylchloride/acrylic acid/methacrylic acid copolymer, etc.; a graftcopolymer containing more than 30% by weight of vinyl chloride, such asan ethylene/vinyl acetate/vinyl chloride graft copolymer; apost-chlorinated polyvinyl chloride; and a blend of two or more of theabove described materials.

Post chlorinated polyethylene is a rubbery or plastic material preparedby post-chlorinating polyethylene and, it is well known to blendpost-chlorinated polyethylene with vinyl chloride to improve impactresistance and weatherability, to blend post-chlorinated polyethylenewith rubber to improve ozone resistance, weatherability, chemicalresistance, heat resistance, etc., and to blend post-chlorinatedpolyethylene with an olefinic polymer to improve low-temperature impactresistance and to provide thereto flame resistance.

As previously described, the co-extrusion method, theextrusion-lamination method, the press method and the like can bepractically employed as the heat sealing method for polyvinyl chlorideand an olefinic polymer. When co-extrusion of the composite material isemployed, an extrusion temperature of not more than 220° C. and a dietemperature of not more than 210° C. are preferred. Whenextrusion-lamination is employed, it is desired that the olefinicpolymer be extruded and laminated substantially simultaneously. Furtherwhen the press method is employed, the press temperature is desirablyset at not more than 210° C. In this process, if the temperature is setat more than 210° C., polyvinyl chloride is thermally decomposed and adeterioration in efficiency can be expected.

The composite materials prepared by the present invention are veryuseful for packaging. For example, in this method, the contents to bepackaged are packed in an evacuated container or rigid polyvinylchloride and then heat sealing is conducted using as a sealing materialthe adhesive material of this invention.

Post-chlorinated polyethylene can be added to polyvinyl chloride by amanner similar to the techniques used in blending various conventionaladditives and no special techniques need be used.

As described above, the liquid adhesive of this invention comprises thesolid adhesive of this invention in a suitable solvent. Examples ofsuitable solvents which can be employed in the liquid adhesivecomposition of this invention are aromatic hydrocarbons such as benzene,toluene and the like, chlorinated organic compounds such as carbontetrachloride, trichloroethylene, tetrachloroethylene,tetrachloroethane, chlorobenzene and the like, tetrahydrofuran, methylethyl ketone, cyclohexanone and the like. Further, a mixture of solventscan be optionally employed. The amount of the solvent generally used isabout 98 to 70% by weight, preferably 95 to 80% by weight, in the liquidadhesive. The post-chlorinated polyethylene is not always completelydissolved in the organic solvent, and the adhesive of this invention canbe suitably employed in the form of a uniform gel condition or a uniformswelled condition.

Also, the adhesive composition of this invention can containadditionally materials which are conventionally used for improving theproperties and processability of polyvinyl chloride. For example,processing aids, modifiers, stabilizers, lubricants, pigments,reinforcing agents, plasticizers, extenders, antioxidants and the likecan be added in a small proportion to the composition of this invention.

The features of the co-extruded composite material of polyvinyl chlorideand the olefinic polymer according to the present invention are asfollows: That is, the production cost for the composite material isquite low since the two polymers having different properties can be heatsealed to each other in one step. The composite material having both gasbarrier characteristics and steam barrier characteristics is obtained bycompositing a vinyl chloride resin having excellent gas barriercharacteristics and an olefinic polymer having excellent moisture proofproperties. Moreover, since the composite material of thus invention iscomposed of a layer of polyvinyl chloride resin and a layer of anolefinic polymer, other materials which can be heat sealed with theolefinic polymer but cannot be heat sealed with the polyvinyl chlorideresin or other materials which can be heat sealed with the polyvinylchloride resin but cannot be heat sealed with the olefinic polymer canbe heat sealed with the composite material of this invention byselecting the appropriate surface to be heat sealed depending on thematerial to which the composite is to be adhered.

According to the present invention a multi-layer composite materialhaving three or more polymeric layers can be produced by co-extrusion.For example, a five-layer composite material composed of a centralolefinic polymer layer, intermediate polyvinyl chloride layers heatsealed to both surfaces of the central olefinic polymer layer, and outerlayers of a material which can be heat sealed with the polyvinylchloride but cannot be heat sealed with the olefinic polymer, theseouter layer being heat sealed to the outer surfaces of the intermediatepolyvinyl chloride layers, can be prepared by co-extrusion in one step.Also, a five-layer composite material composed of a central polyvinylchloride layer, intermediate olefinic polymer layers, and outer layersof a material which can be heat sealed with the olefinic polymer butcannot be heat sealed with the polyvinyl chloride can be prepared byco-extrusion.

The composite materials prepared by the present invention can be usedfor various purposes such as food packaging, packaging of tablets ofmedicaments or chemicals, etc.

The following examples are intended to illustrate specifically thepresent invention but not to limit the present invention in any way. Inthe examples all parts and percents are by weight unless otherwiseindicated.

EXAMPLE 1

Polyvinyl chloride having a polymerization degree of 400 andnon-crystalline post-chlorinated polyethylene having a mean molecularweight of about 40,000 and a chlorine content of 30% were dissolved inthe solvent as shown in the following table in the ratio as shown in thesame table.

    ______________________________________                                                1     2       3       4     5     6                                   ______________________________________                                                (parts by weight)                                                     Polyvinyl                                                                     Chloride  100     100     100    50    10   0                                 Post-chlorinat-                                                               ed Polyethylene                                                                         0       3        30    50   100   100                               Ca-Zn Type                                                                    Metal Soap                                                                              2       2       2     1     0.2   0                                 Methyl Ethyl                                                                  Ketone    500     500     500   500   500   500                               Tetrahydrofuran                                                                         500     500     500   500   500   500                               ______________________________________                                    

Each of the adhesives thus prepared was applied to an aluminum foilhaving a thickness of 25 microns using an applicator and dried. Then,the aluminum foil having the adhesive layer was heat sealed to alow-density polyethylene film having a thickness of 80 microns. In thiscase, the aluminum foil side was placed toward the hot plate of the heatsealing machine and the heat sealing was conducted under the followingconditions:

    ______________________________________                                        Temperature of the Hot Plate:                                                                      150° C.                                           Pressure Applied:     2 kg/cm.sup.2                                           Heat Seal Period of Time:                                                                           1.0 second.                                             ______________________________________                                    

In addition, the polyethylene film used above was not subjected to anysurface treatment, such as a corona-discharge treatment.

When the heat sealed samples prepared were subjected to a peeling testaccording to the method of ASTM-D-1876-61T, the results shown in Table 1were obtained.

                  Table 1                                                         ______________________________________                                                 1   2       3       4     5     6                                    ______________________________________                                        Peel Strength                                                                            0     0.2     0.9   1.5   1.7   1.5                                (kg/inch)                                                                     ______________________________________                                    

EXAMPLE 2

After applying the adhesive as used in Example 1 to an aluminum foilfollowed by drying as described in Example 1, a rigid polyvinyl chloridesheet having a thickness of 200 microns was heat sealed to the foilunder the following conditions:

    ______________________________________                                        Hot Plate Temperature:                                                                             160° C.                                           Pressure Applied:     4 kg/cm.sup.2                                           Heat Seal Period of Time:                                                                           2 seconds.                                              ______________________________________                                    

When the samples thus prepared were subjected to the peeling test asdescribed in Example 1, the results shown in the following table wereobtained.

                  Table 2                                                         ______________________________________                                                 1   2       3       4     5     6                                    ______________________________________                                        Peel Strength                                                                            4.5   4.7     5.5   5.8   4.3   3.0                                (kg/inch)                                                                     ______________________________________                                    

EXAMPLE 3

Polyvinyl chloride containing 5% vinyl acetate and having a meanpolymerization degree of 400 and non-crystalline post-chlorinatedpolyethylene having a mean molecular weight of about 40,000 and achlorine content of 35% were dissolved in the solvent as shown in thefollowing table in the ratio shown in the same table.

    ______________________________________                                                  7    8      9       10    11    12                                  ______________________________________                                        Polyvinyl Chloride                                                                        100    100    100    50    10   0                                 containing 5%                                                                 Vinyl Acetate                                                                 Post-chlorinated                                                                          0      3       30    50   100   100                               Polyethylene                                                                  Ca-Zn Type Metal                                                                          2      2      2     1     0.2   0                                 Soap                                                                          Toluene     500    500    500   500   500   500                               Ethyl Acetate                                                                             500    500    500   500   500   500                               ______________________________________                                    

After applying the adhesive thus prepared to a rigid polyvinyl chloridesheet having a thickness of 250 microns using an applicator followed bydrying, a low-density polyethylene film having a thickness of 80microns, which had not be subjected to any surface treatment, was heatedsealed to the polyvinyl chloride sheet under the following conditions:

    ______________________________________                                        Hot Plate Temperature:                                                                             150° C.                                           Pressure Applied:     2 kg/cm.sup.2                                           Heat Seal Period of Time:                                                                           2 seconds.                                              ______________________________________                                    

Then, when the samples thus heat sealed were subjected to the peelingtest according to the method of ASTM-D-1876-61T, the results shown inthe following table were obtained.

                  Table 3                                                         ______________________________________                                                 7   8       9       10    11    12                                   ______________________________________                                        Peel Strength                                                                            0     0.3     1.2   1.8   1.6   1.3                                (kg/inch)                                                                     ______________________________________                                    

EXAMPLE 4

After applying the adhesive as used in Example 3 to a 6-nylon filmhaving a thickness of 80 microns, which had not been subjected to anysurface treatment, followed by drying, a rigid polyvinyl chloride sheethaving a thickness of 250 microns or a polyethylene sheet having athickness of 250 microns was heat sealed to the 6-nylon film under thefollowing conditions:

    ______________________________________                                        Hot Plate Temperature:                                                                             220° C.                                           Pressure Applied:     2 kg/cm.sup.2                                           Heat Seal Period of Time:                                                                           2 seconds.                                              ______________________________________                                    

When the samples thus heat sealed were subjected to the peeling test asdescribed in Example 3, the results shown in Table 4 were obtained.

                  Table 4                                                         ______________________________________                                        Peeling Test Results                                                          (kg/inch)                                                                                7   8       9       10    11   12                                  ______________________________________                                        6-Nylon Polyvinyl                                                                          0     0.1     0.8   2.7   2.9  3.0                               chloride                                                                      6-Nylon/Polyethylene                                                                       0     0.1     0.3   1.1   1.5  1.8                               ______________________________________                                    

EXAMPLE 5

Two sheets of films, each having a thickness of 50 microns, wereprepared using the two kinds of the resin compositions respectivelyshown in the following table using a calender roller of 18 inches:

    ______________________________________                                                          13     14                                                   ______________________________________                                        Polyvinyl Chloride  100     100                                               (mean polymerization                                                          degree 800)                                                                   Post-chlorinated Poly-                                                                             20     0                                                 ethylene (mean molecular                                                      weight, about 45,000;                                                         Cl-content, 30%)                                                              Ca-Zn Type Metal Soap                                                                             2       2                                                 Stearic Acid (lubricant)                                                                          2       2                                                 Epoxidized Soybean Oil                                                                            2       2                                                 ______________________________________                                    

Then, each of the films prepared above was sandwiched between a 6-nylonfilm having a thickness of 80 microns, which was not subjected to anysurface treatment, and a rigid polyvinyl chloride film having athickness of 100 microns and they were heat sealed under the followingconditions:

    ______________________________________                                        Hot Plate Temperature:                                                                             220° C.                                           Pressure Applied:    2 kg/cm.sup.2                                            Heat Seal Period of Time:                                                                          2 seconds.                                               ______________________________________                                    

    ______________________________________                                        Hot Plate Temperature:                                                                             220° C.                                           Pressure Applied:     2 kg/cm.sup.2                                           Heat Seal Period of Time:                                                                           2 seconds.                                              ______________________________________                                    

Then, when a peeling test was conducted between the 6-nylon film and therigid polyvinyl chloride film of the heat sealed samples according tothe method of ASTM-D-1876-61T, the results shown in the following tablewere obtained.

                  Table 5                                                         ______________________________________                                                           13    14                                                   ______________________________________                                        Peel Strength (kg/inch)                                                                             1.7     0                                               ______________________________________                                    

The results showed that the film composed of the blend ofpost-chlorinated polyethylene and polyvinyl chloride was effective foradhering the 6-nylon film and the rigid polyvinyl chloride film as afilm-form adhesive.

EXAMPLE 6

Heat sealing procedures were conducted under the heat sealing conditionsas described in Example 5 using the film-form adhesive as used inExample 5. The films heat sealed using the film-form adhesive were shownin the following table. The results obtained of the peeling test of theheat sealed samples are shown in the same table.

                  Table 6                                                         ______________________________________                                                          13    14                                                    ______________________________________                                        Rigid Polyvinyl Chloride                                                      (thickness of 100μ)                                                                            2.5     0                                                 Low-density Polyethylene                                                      (thickness of 80 μ)                                                        Rigid Polyvinyl Chloride                                                      (thickness of 100 μ)                                                                           4.3     0                                                 Aluminum Foil                                                                 (thickness of 25 μ)                                                        Low-density Polyethylene                                                      (thickness of 80 μ)                                                                            0.8     0                                                 Aluminum Foil                                                                 (thickness of 25 μ)                                                        6-Nylon                                                                       (thickness 80 μ) 0.4     0                                                 Low-density Polyethylene                                                      (thickness of 80 μ)                                                        ______________________________________                                    

EXAMPLE 7

Each of four kinds of vinyl chloride coplymers and noncrystallinepost-chlorinated polyethylene having a mean molecular weight of about30,000 and a chlorine content of 35% were dissolved in the solvent asshown in the following table to provide four kinds of adhesives. Thevinyl chloride copolymers used in the above procedures were as follows:

Adhesive No. 15: Vinyl chloride copolymer having an apparent meanpolymerization degree of about 400 and containing 1% ethylene.

Adhesive No. 16: Vinyl chloride copolymer having an apparent meanpolymerization degree of about 450 and containing 10% acrylic acid.

Adhesive No. 17: Ethylene/vinyl acetate/vinyl chloride graft copolymerhaving a mean polymerization degree of about 800, (Sumigraft GB, tradename, produced by Sumitomo Chemical Co., Ltd.)

Adhesive No. 18: Chlorinated polyvinyl chloride having an apparent meanpolymerization degree of about 700 and containing 65% chlorine.

    ______________________________________                                                         15    16      17     18                                      ______________________________________                                        Vinyl Chloride Copolymer                                                                         100     100     100  100                                   Post-chlorinated Polyethylene                                                 (mean molecular weight, about                                                                     20      20      20   20                                   30,000; chlorine content, 35%)                                                Ca-Zn Type Metal Soap                                                                            2       2       2    2                                     Methyl Ethyl Ketone                                                                              500     500     500  500                                   Tetrahydrofuran    500     500     500  500                                   ______________________________________                                    

After applying each of the adhesives to a 6-6-nylon sheet having athickness of 50 microns, which had not been subjected to any surfacetreatment, using an applicator followed by drying a rigid polyvinylchloride sheet having a thickness of 250 microns was heat sealed to thenylon sheet in the case of using adhesive No. 15, a polypropylene sheethaving a thickness of 100 microns was heat sealed in the case of usingadhesive No. 16, an ethylene acrylic acid copolymer sheet having athickness of 50 microns was heat sealed in the case of using adhesiveNo. 17, and an ethylene/sodium methacrylate ionomer sheet having athickness of 50 microns in the case of using adhesive No. 18. The heatseal conditions were as follows:

    ______________________________________                                        Hot Plate Temperature:                                                                             220° C.                                           Pressure Applied:     2 kg/cm.sup.2                                           Heat Seal Period of Time:                                                                           2 seconds.                                              ______________________________________                                    

Thereafter, the peel strength in each case was measured, the results ofwhich were shown in the following table.

                  Table 7                                                         ______________________________________                                                    15    16      17      18                                          ______________________________________                                        Peel Strength 0.8     0.5     1.4   0.7                                       (kg/inch)                                                                     ______________________________________                                    

EXAMPLE 8

The following eight kinds of films each having a thickness of 50 micronswere prepared using a calender roller of 18 inches. Then, each of theadhesive films was sandwiched between the specific films and after heatsealing them, the peel strength was measured in each case. The resultsobtained are shown in the following table together with the compositionsof the adhesive films used.

                                      Table 8                                     __________________________________________________________________________                 19      20      21      22                                       __________________________________________________________________________                 a   b   a   b   a   b   a   b                                    __________________________________________________________________________    Vinyl Chloride                                                                             100 100 100 100 100 100 100 100                                  Copolymer*                                                                    Post-chlorinated                                                                           20  0   20  0   20  0   20  0                                    Polyethylene                                                                  (mean molecular                                                               weight, about 30,000;                                                         chlorine content, 35%)                                                        Ca-Zn Type Metal                                                                           2   2   2   2   2   2   2   2                                    Soap                                                                          Stearic Acid 2   2   2   2   2   2   2   2                                    (lubricant)                                                                   Epoxidized Soy-                                                                            2   2   2   2   2   2   2   2                                    bean Oil                                                                      Specific Films**                                                                           A   A   B   B   C   C   D   D                                                 E   E   E   E   F   F   G   G                                    Peel Strength                                                                              2.0 0   2.4 0   0.9 0   0.5 0                                    (kg/inch)                                                                     __________________________________________________________________________     Note:                                                                         (*)Adhesive No. 19: Vinyl chloride copolymer having an apparent average       polymerization degree of about 750 and containing 1% ethylene.                Adhesive No. 20: Vinyl chloride copolymer having an apparent average          polymerization degree of about 800 and containing 10% acrylic acid.      

Note:

(*): Adhesive No. 19: Vinyl chloride copolymer having an apparentaverage polymerization degree of about 750 and containing 1% ethylene.

Adhesive No. 20: Vinyl chloride copolymer having an apparent averagepolymerization degree of about 800 and containing 10% acrylic acid.

Adhesive No. 21: Ethylene/vinyl acetate/vinyl chloride graft copolymerhaving a mean polymerization degree of about 1,000, (Sumigraft GA, tradename, produced by Sumitomo Chemical Co., Ltd.).

Adhesive No. 22: Chlorinated polyvinyl chloride having an apparent meanpolymerization degree of about 700 and containing 65% chlorine.

(**):

Film A: A film of a blend of 15% of polyethylene and 85% ofpolypropylene having a thickness of 150 microns.

Film B: A film of a blend of 10% of a copolymer of 90% ethylene and 10%vinyl acetate and of 90% of a polyethylene having a thickness of 100microns.

Film C: A film of polybutene-1 having a thickness of 100 microns.

Film D: A film of 6-10-nylon having a thickness of 50 microns.

Film E: A film of polyvinyl chloride having a thickness of 250 microns.

Film F: A film of chlorinated polyvinyl chloride having a thickness of250 microns.

Film G: A film of a blend of 97% of polyvinyl chloride and 3% ofpolypropylene having a thickness of 250 microns.

EXAMPLE 9

The polyvinyl chloride compositions as shown in Table 9 were fabricatedinto sheets using a conversed L-type calender roller of 16 inches.

                  Table 9                                                         ______________________________________                                                      Run No.                                                                       1    2      3      4     5                                      ______________________________________                                        Polyvinyl Chloride                                                                            100    100    100  0     100                                  (mean polymerization                                                          degree 700)                                                                   5% Vinyl Acetate-                                                                             0      0      0    100   0                                    Vinyl Chloride Copolymer                                                      (mean polymerization                                                          degree 650)                                                                   Post-chlorinated                                                                              0      2       20   20    50                                  Polyethylene (mean                                                            molecular weight, about                                                       38,000; chlorine content,                                                     40%)                                                                          Ca-Zn Type Metal Soap                                                                         2      2      2    2     2                                    (stabilizer)                                                                  Epoxidized Soybean Oil                                                                        3      3      3    3     3                                    Stearic Acid    2      2      2    2     2                                    (lubricant)                                                                   ______________________________________                                    

Each of the sheets thus prepared was heat sealed to the polyethylenesurface of a laminated film composed of a polyethylene terephthalatefilm having a thickness of 25 microns and a high-pressure processpolyethylene film having a thickness of 60 microns prepared by extrusionunder the following conditions.

    ______________________________________                                        Hot Plate Temperature:                                                                             220° C.                                           Pressure Applied:     2 kg/cm.sup.2                                           Heat Seal Period of Time:                                                                           2 seconds.                                              ______________________________________                                    

Then, a peal strength of each of the heat sealed samples was measuredusing the method of ASTM-D-1876-61T, the results of which were shown inthe following table.

                  Table 10                                                        ______________________________________                                                 Run No.                                                                       1   2        3        4      5                                       ______________________________________                                        Peel Strength                                                                            0     0.3      1.8    2.2    2.5                                   (kg/inch)                                                                     ______________________________________                                    

The above results showed that the polyvinyl chloride resin blended withpost-chlorinated polyethylene could be heat sealed with a polyethylenefilm.

The properties of the resin compositions shown in Table 9 are shown inTable 11.

                                      Table 11                                    __________________________________________________________________________                          Run No.                                                        I*   Units II* 1    2    3    4     5                                  __________________________________________________________________________    Tensile                                                                              ASTM-                                                                              kg/cm.sup.2                                                                         (i)*                                                                              6.2  6.0  5.6  5.7   4.0                                Strength                                                                             D-638      (ii)                                                                              6.0  5.8  5.4  5.4   3.8                                Elongation                                                                           ASTM-                                                                              %     (i)*                                                                              46   55   74   94    152                                       D-638      (ii)                                                                              53   57   92   107   136                                Izod Impact                                                                          ASTM-                                                                              ft-lb/                                                                              --  0.8  1.0  4.2  3.8   6.3                                Strength                                                                             D-256                                                                              inch                                                              Vicat Sof-                                                                           ASTM-                                                                              ° C.                                                                         --  91.0 90.3 87.5 86.0  91.3                               tening Point                                                                         D-1525                                                                 Percent                                                                              ASTM-                                                                              %     --  90.9 90.7 86.5 87.2  70.3                               Transmission                                                                         D-1003                                                                 Moisture                                                                             ASTM-                                                                              g/m.sup.2 -                                                                         --  2.8  2.9  2.7  3.0   2.6                                Permeability                                                                         E-96 24 hrs.                                                           __________________________________________________________________________     (Note):                                                                       (I): Measurement Method                                                       (II): Direction (i): Parallel Direction; (ii): Vertical Direction        

The results showed that the polyvinyl chloride compositions containing 2to 50 parts of chlorinated polyethylene clearly had the properties ofpolyvinyl chloride and could be heat sealed with polyethylene as statedabove.

EXAMPLE 10

A two-layer extrusion type film forming apparatus composed of anextruder I having an inside diameter of 90 mm. and an extruder II havingan inside diameter of 50 mm in which the melts from the extruders werecombined through two manifolds and welded in the same die was used.Low-density polyethylene having a melt index of 1.0 was melt-extrudedthrough the extruder II to form a film thereof having a thickness ofabout 100 microns and the vinyl chloride resin composition as shown inTable 12 was melt-extruded through the extruder to form a thickness ofabout 500 microns, whereby a two-layer extruded film was prepared.

                  Table 12                                                        ______________________________________                                                            Run No.                                                                       6       7                                                 ______________________________________                                        Polyvinyl Chloride    100      100                                            (mean polymerization degree 700)                                              Post-chlorinated Polyethylene                                                                       0         20                                            (mean molecular weight,                                                       about 30,000; chlorine content 30%)                                           Octyltin-type Stabilizer                                                                            3.5      3.5                                            Epoxidized Soybean Oil                                                                              4.0      4.0                                            Alkylphenol-type Antioxidant                                                                        0.4      0.4                                            Stearic Acid (lubricant)                                                                            2.0      2.0                                            Butyl Stearate Ester  0.8      0.1                                            ______________________________________                                    

After cooling, the adhesion of the laminate film was measured. Theresults showed that the composite film of Run No. 6 was readilyseparated into two layers, while the composite film of Run No. 7 couldnot readily be separated each other. Thus, 11 lattice cuts were formedin the polyethylene film side of the composite film in a depth deeperthan the thickness of the polyethylene film layer with a distance of 2mm using a sharp edge and after applying an adhesive tape to the surfaceof the cut-formed layer of the composite film and manually pressing theadhesive tape, the adhesive tape was separated manually. No lattice-cutpolyethylene layers were carried by the adhesive tape, which showed thatthe two heat sealed layers of the composite film of Run No. 7 hadsufficient adhesive strength.

This example showed that a heat sealed composite sheet of polyvinylchloride and an olefinic polymer could be prepared by a co-extrusionmethod, which has never been attained using conventional techniques.

EXAMPLE 11

Each of the polyvinyl chloride (mean polymerization degree of 700)compositions shown in Table 13 was fabricated into a sheet having athickness of 250 microns using a calender roller.

                  Table 13                                                        ______________________________________                                                        Run No.                                                                       8         9                                                   ______________________________________                                        Polyvinyl Chloride                                                                              100    parts   100   parts                                  Post-chlorinated Polyethylene                                                                    20    "       0                                            (mean molecular weight, about                                                 30,000; chlorine content 30%)                                                 Ca-Zn-type Stabilizer                                                                           2      "       2     "                                      Epoxidized Soybean Oil                                                                          3      "       3     "                                      Stearic Acid (lubricant)                                                                        2      "       2     "                                      ______________________________________                                    

Then, each of the following three kinds of olefinic polymers wasextruded into a sheet having a thickness of 50 microns using anextruder.

1. Polyethylene

2. A blend of 90% of polyethylene and 10% of a ethylene/vinyl acetatecopolymer.

3. Ionomer of ethylene and sodium acrylate.

Each of the films thus prepared and the film of Run No. 8 or Run No. 9were passed through a press roll to form a composite film.

The two polymer layers of the laminate of Run No. 9 were readilyseparated after cooling, while the polymer layers of the laminate of RunNo. 8 were not separated even using the adhesive tape test as in Example10.

EXAMPLE 12

Each of the compositions shown in the following table was fabricatedinto a sheet having a thickness of 500 microns using a calender roller.

                  Table 14                                                        ______________________________________                                                        Run No.                                                                       10   11      12      13                                       ______________________________________                                        Polyvinyl Chloride                                                            (mean polymerization degree                                                                     100    100     0     0                                      about 1,000)                                                                  Vinyl Chloride Copolymer                                                      containing 5% Vinyl Acetate                                                                     0      0       100   100                                    (mean polymerization degree                                                   about 800)                                                                    Post-Chlorinated Polyethylene                                                 (mean molecular weight, about                                                                   0       30     0      30                                    30,000; chlorine content                                                      about 35%)                                                                    Phthalic Acid Type Plasticizer                                                                   10     10      10    10                                    Pb-Type Stabilizer                                                                              3      3       3     3                                      Stearic Acid (lubricant)                                                                        2      2       2     2                                      ______________________________________                                    

The above-described sheets were piled to form a laminate having athickness of 10 mm and then after placing a polyethylene sheet having athickness of 1 mm on the laminate, they were pressed under the followingconditions.

    ______________________________________                                        Hot Plate Temperature  180° C.                                         Pressure Applied:      100 kg/cm.sup.2                                        Pressing Period of Time:                                                                              10 minutes                                            ______________________________________                                    

The area of the laminate was 1 m × 1 m

When the composite product was cooled and withdrawn, the polyethylenesheet was readily separated from the polyvinyl chloride sheet in Run No.10 and Run No. 12, while the polyethylene sheet was not separatedmanually from the polyvinyl chloride sheet in Run No. 11 and Run No. 13.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A method of adhering polyvinyl chloride and an olefinic polymer which comprises co-extruding three layers of a polyvinyl chloride, an adhesive and an olefinic polymer to produce a three-layered laminate of, in order of layers, polyvinyl chloride, adhesive and olefinic polymer, said adhesive comprisinga. 1 to 99% by weight of post-chlorinated polyethylene having a specific gravity of 1.00 to 1.35, a chlorine content of 5 to 50% and a mean molecular weight of from about 20,000 to 200,000, and b. 99 to 1% by weight of polyvinyl chloride having a mean degree of polymerization of from about 300 to 2,500.
 2. A method of adhering polyvinyl chloride and an olefinic polymer which comprises pressing three layers, in order of layers, a polyvinyl chloride, an adhesive and an olefinic polymer to produce a three-layered laminate of, in order of layers, polyvinyl chloride, adhesive and olefinic polymer, said adhesive comprisinga. 1 to 99% by weight of post-chlorinated polyethylene having a specific gravity of 1.00 to 1.35, a chlorine content of 5 to 50% and a mean molecular weight of from about 20,000 to 200,000, and b. 99 to 1% by weight of polyvinyl chloride having a mean degree of polymerization of from about 300 to 2,500.
 3. A method of adhering polyvinyl chloride and an olefinic polymer which comprises heat-sealing three layers of, in order of layers, a polyvinyl chloride, an adhesive and an olefinic polymer to produce a three-layered laminate of, in order of layers, polyvinyl chloride, adhesive and olefinic polymer, said adhesive comprisinga. 1 to 99% by weight of post-chlorinated polyethylene having a specific gravity of 1.00 to 1.35, a chlorine content of 5 to 50% and a mean molecular weight of from about 20,000 to 200,000, and b. 99 to 1% by weight of polyvinyl chloride having a mean degree of polymerization of from about 300 to 2,500.
 4. A method of adhering polyvinyl chloride and an olefinic polymer which comprises coating a liquid adhesive on at least one surface of polyvinyl chloride or olefinic polymer followed by drying said adhesive, and pressing said polyvinyl chloride and said olefinic polymer with the adhesive in between to produce a three-layered laminate of polyvinyl chloride, adhesive and olefinic polymer, said adhesive comprisinga. 1 to 99% by weight of post-chlorinated polyethylene having a specific gravity of 1.00 to 1.35, a chlorine content of 5 to 50% and a mean molecular weight of from about 20,000 to 200,000 and b. 99 to 1% by weight of polyvinyl chloride having a mean degree of polymerization of from about 300 to 2,500 in a solvent.
 5. A method of adhering polyvinyl chloride and an olefinic polymer which comprises coating a liquid adhesive on at least one surface of polyvinyl chloride or olefinic polymer followed by drying said adhesive, and heat sealing said polyvinyl chloride and said olefinic polymer with the adhesive in between to produce a three-layered laminate of polyvinyl chloride, adhesive and olefinic polymer, said adhesive comprisinga. 1 to 99% by weight of post-chlorinated polyethylene having a specific gravity of 1.00 to 1.35, a chlorine content of 5 to 50% and a mean molecular weight of from about 20,000 to 200,000, and b. 99 to 1% by weight of polyvinyl chloride having a mean degree of polymerization of from about 300 to 2,500 in a solvent.
 6. A method of adhering polyvinyl chloride and olefinic polymer which comprises coating a liquid adhesive on at least one surface of polyvinyl chloride or olefinic polymer followed by drying said adhesive, and extruding either said polyvinyl chloride and said olefinic polymer which has not been coated with the adhesive layer to produce a three-layered laminate, in order of layers, of polyvinyl chloride, adhesive and olefinic polymer, said adhesive comprisinga. 1 to 99% by weight of post-chlorinated polyethylene having a specific gravity of 1.00 to 1.35, a chlorine content of 5 to 50% and a mean molecular weight of from about 20,000 to 200,000, and b. 99 to 1% by weight of polyvinyl chloride having a mean degree of polymerization of from about 300 to 2,500 in a solvent.
 7. A three-layered composite material prepared by the method according to claim
 1. 8. A three-layered composite material prepared by the method according to claim
 2. 9. A three-layered composite material prepared by the method according to claim
 3. 10. A three-layered composite material prepared by the method according to claim
 4. 11. A three-layered composite material prepared by the method according to claim
 5. 12. A three-layered composite material prepared by the method according to claim
 6. 13. The method according to claim 1, wherein said adhesive comprises 2 to 50 parts by weight of post-chlorinated polyethylene and 100 parts by weight of polyvinyl chloride.
 14. The method according to claim 2, wherein said adhesive comprises 2 to 50 parts by weight of post-chlorinated polyethylene and 100 parts by weight of polyvinyl chloride.
 15. The method according to claim 3, wherein said adhesive comprises 2 to 50 parts by weight of post-chlorinated polyethylene and 100 parts by weight of polyvinyl chloride.
 16. The method according to claim 4, wherein the liquid adhesive has an amount of solvent of about 98 to 70% by weight in the liquid adhesive.
 17. The method according to claim 15, wherein the liquid adhesive has an amount of solvent of about 98 to 70% by weight in the liquid adhesive.
 18. The method according to claim 6, wherein the liquid adhesive has an amount of solvent of about 98 to 70% by weight in the liquid adhesive.
 19. The method according to claim 4, wherein said liquid adhesive comprises 2 to 50 parts by weight of post-chlorinated polyethylene 100 parts by weight of polyvinyl chloride and a solvent.
 20. The method according to claim 5, wherein said liquid adhesive comprises 2 to 50 parts by weight of post-chlorinated polyethylene, 100 parts by weight of polyvinyl chloride and a solvent.
 21. The method according to claim 6, wherein said liquid adhesive comprises 2 to 50 parts by weight of post-chlorinated polyethylene, 100 parts by weight of polyvinyl chloride and a solvent. 